KR20120078651A - Photoacid generaing monomer and precursor thereof - Google Patents

Abstract

PURPOSE: A photoacid-generating monomer compound is provided to have low diffusion properties, and low outgassing properties, and to able to provide high contrast and good line shape. CONSTITUTION: A photoacid-generating monomer compound is in chemical formula 1. In chemical formula 1, R1, R2, and R3 is independently H, F, C1-10 alkyl, fluoro-substituted C1-10 alkyl, C1-10 cycloalkyl, or fluoro-substituted C1-10 cycloalkyl, but at least one of R1, R2, or R3 is F, n is an integer from 1-10. A is a halogenated or non-halogenated C2-30 olefin-containing polymerizable group, G+ is an organic or inorganic cation. Sultone precursor for monomer in chemical formula 1 is expressed by chemical formula 18.

Description

Photoacid Generating Monomers and Precursors thereof {PHOTOACID GENERAING MONOMER AND PRECURSOR THEREOF}

This application is the main application of US Provisional Application No. 61 / 428,999, filed December 31, 2010, the contents of which are incorporated herein by reference in their entirety.

Polymerizable photoacid generating monomers, and sultone precursor compounds for the monomers are disclosed.

Advanced photolithographic techniques for imprinting desired patterns on silicon wafers are generally poly (methacrylate) photoresist polymers as an important chemical reaction in transferring patterns to induce solubility changes. The heavy ester is followed by acid-catalyzed deprotection with acid. The catalytic process, referred to as chemical amplification, is caused by the irradiation of photosensitive reagents or photoacetic generators (PAGs). PAGs used in photoresist polymers may consist of two parts: a sulfonate anion, and a tris (hydrocarbyl) sulfonium cation, typically having at least one aromatic group, where the cation absorbs photons Decomposition results in one acid proton, which causes a number of desirable acid-catalyzed chemical reactions. Sulfonic acid superacids, for example alkyl or arylsulfonic acids, which generally have a fluorine substituent within the two or three bond lengths of a sulfur atom, are preferred in some applications.

As the advances in photolithography technology become increasingly finer patterns, acid diffusion in photoresist matrices is of concern. Acid diffusion can be delayed in one way by tethering the conjugated base of the acid (eg, sulfonate anion) to the polymer, restricting the acid to a limited volume, and more evenly distributing the PAG into the photoresist matrix. have.

US Published Patent Publication No. 2009/0202943 A1 discloses acrylates or methacrylates having photoactive sulfonium fluoroalkylsulfonate salts (i.e. conjugated bases of superacids) tethered thereto via (meth) acrylate monomer linkages. Positive-tone resists are disclosed that include polymers made from monomers. One example of such a monomer is prepared by condensation of a triaryl sulfonium salt of 1,1-difluoro-2-hydroxyethylsulfonate with (meth) acrylic anhydride. While such condensation reactions can in principle be used, the synthesis of anions involves three stage synthesis from commercially available precursors, which are limited by the possibility of side reactions with cations and / or polyfunctional anions.

These and other disadvantages of the prior art can be overcome by compounds having formula (I):

In the above formula

R ¹ , R ² , and R ³ independently of one another are H, F, C _1-10 alkyl, fluoro-substituted C _1-10 alkyl, C _1-10 cycloalkyl, or fluoro-substituted C _{1- 10} cycloalkyl, provided that at least one of R ¹ , R ² , and R ³ is F;

n is an integer from 1 to 10;

A is a halogenated or non-halogenated C _2-30 olefin-containing polymerizable group;

G ⁺ is an organic or inorganic cation.

The polymer comprises a compound of formula (I).

Sultone precursors for monomers have formula (XVI):

In the above formula

R is independently of each other F, C _1-10 alkyl, fluoro-substituted C _1-10 alkyl, C _1-10 cycloalkyl, or fluoro-substituted C _1-10 cycloalkyl, provided that at least one R is F;

n is an integer from 0 to 10;

m is an integer from 1 to 4 + 2n.

The monomer comprises the reaction product of the sultone precursor with an oxyanion of a hydroxy-containing or carboxy-containing halogenated or non-halogenated C _2-30 olefin-containing compound.

The foregoing and other objects, features, and advantages of the present invention will become apparent from the following detailed description taken in conjunction with the accompanying drawings, wherein
1 shows a thermogravimetric plot of mass loss versus temperature for exemplary monomers;
2 is an ORTEP plot of potassium salts of exemplary monomers based on X-ray crystallographic analysis;
FIG. 3 shows deep ultraviolet (DUV) as a plot of feature size (in angstroms) versus exposure dose (in milli Joules per square centimeter, mJ / cm 2) for polymers made using exemplary photoacid generator monomers. Lithography contrast curve.

Disclosed herein are sultone precursors for monomers, and novel olefinic monomers useful as photoacid generators (here PAGs) from fluorinated sultone precursors. As used herein, "sultone" refers to a cyclic sulfonate ester that can be subjected to a ring-opening attack by adding nucleophiles, where the ring-opening nucleophilic attack is directed to sultone ring oxygen. Specific for the carbon atom alpha. Preferably, the sultone is fluorinated with at least one fluorine atom, and even more preferably, the sultone may comprise a geminal difluoromethylene group alpha relative to the sulfonate sulfur atom. If the nucleophile used in the ring opening reaction is a carboxylic acid such as (meth) acrylic acid, or hydroxystyrene or hydroxymethyl styrene, the reaction product with sultone may be useful as a monomer for radical polymerization. In these examples the nucleophile may be an oxygen anion of one of these compounds, having a base and (meth) acrylic acid or styrene carboxylic acid, hydroxystyrene (having phenolic group) or hydroxymethylstyrene (benzyl alcohol residue) It can be prepared by the reaction with).

Thus, the ring-opened product of sultone is obtained very neatly in high yield. Photoacid generators with low diffusivity and low outgassing properties are also prepared from ring-opened products by metathesis in which the cation of the ring-opened product is exchanged with a photoactive cation, such as an onium cation having at least one phenyl group. Can be. Such monomers are preferably acid upon exposure to radiation for advanced lithography, such as e-beams, x-rays, and extreme ultraviolet (EUV) radiation having wavelengths of 13.4-13.5 nm when polymerized into polymers and used in photoresist compositions. Generates. Such monomers are preferably low in acid diffusivity and can provide high contrast and good line shape. In addition, degradation products of these PAGs can be reduced compared to conventional non-polymeric bonded PAGs under photoresist compositions, exposure and processing under similar conditions.

"Onium" as used herein refers to an iodonium or sulfonium cation. In addition, "substituted" as used herein is halogen (ie, F, Cl, Br, I), hydroxy, amino, thiol, carboxyl, carboxylate, amide, nitrile, thiol, sulfide, disulfide , Nitro, C _1-10 alkyl, C _1-10 alkoxy, C _6-10 aryl, C _6-10 aryloxy, C _7-10 alkyl aryl, C _7-10 alkyl aryloxy, or at least one of the foregoing It means to include a substituent such as a combination containing. It is to be understood that the groups or structures disclosed for the formulas herein may be substituted as described above, unless otherwise specified or where such substitutions obviously adversely affect the desired properties of the resulting structure. Also, as used herein, "(meth) acrylate" means acrylate or methacrylate, and is not limited to one of these unless otherwise specified.

Monomers of the present invention are compounds having formula (I):

In the above formula

R ¹ , R ² , and R ³ independently of one another are H, F, C _1-10 alkyl, fluoro-substituted C _1-10 alkyl, C _1-10 cycloalkyl, or fluoro-substituted C _{1- 10} cycloalkyl, provided that at least one of R ¹ , R ² , and R ³ is F.

Exemplary groups R ¹ , R ² , and R ³ are, in addition to one or more fluorine atoms, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, n-pentyl , 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, n-heptyl, n-octyl, 3-octyl, n-decyl, or trifluoromethyl group, 2,2, The aforementioned alkyl group having one or more fluorine substituents, including 2-trifluoroethyl, perfluoroethyl, perfluorobutyl, and the like; Or cycloalkyl groups such as cyclobutyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 1- or 2-adamantyl, 1- or 2-decalinyl; Or cycloalkyl groups described above having one or more fluorine substituents, including perfluorocyclopentyl, 3,5-bis (trifluoromethyl) cyclohexyl, perfluorocyclohexyl, and the like. More preferably, R ¹ , R ² , and R ³ are independently a combination of H and F.

In formula (I), n is an integer of 1 to 10, preferably n is 1, 2, or 3. Therefore, the total number of substituents R ¹ , R ² , and R ³ (other than hydrogen) in formula (I) may be 4 + 2n. The monomer may comprise only a single R ¹ , R ² , and R ³ non-hydrogen substituent, where the substituent is F, or one or more substituents (other than hydrogen) are included outside the F group. Alternatively, the substituents R ¹ , R ² , and R ³ are not F.

In addition, in formula (I), A is a halogenated or non-halogenated C _2-30 olefin-containing polymerizable group and G ⁺ is an organic or inorganic cation.

In particular, A is the reaction moiety of the nucleophile. The nucleophile may comprise a nucleophilic group capable of reacting with the precursor sultone, which is subsequently initiated, while the nucleophile preferably reacts under polymerization conditions such as radical, anionic, cationic, or controlled free-radical polymerization processes To provide a polymer. Preferably, the nucleophile is an oxygen anion of a hydroxy-containing halogenated or non-halogenated C _2-30 olefin-containing compound, where A is a halogenated or non-halogenated C _2-30 olefin-containing polymerizable group A Reaction residues of nucleophiles that provide

Preferably, the nucleophile is an oxygen anion of C _3-20 vinyl carboxylic acid, hydroxy-containing C _5-20 vinyl carboxylate, or C _7-20 vinyl hydroxyaromatic compound. The hydroxyaromatic compounds used herein may include phenolic hydroxy groups, or non-phenolic hydroxy groups such as benzyl hydroxy groups, or pendant hydroxy groups.

Exemplary nucleophiles include unsaturated carboxylic acids such as (meth) acrylic acid, (meth) acryloyl acetic acid, maleic or fumaric acid, citraconic acid, itaconic acid, hydroxyl-containing (meth) acrylate esters, such as 2- Hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, carboxylic acids of norbornene, such as 5-norbornene-2-carboxylic acid and 5-norbornene-2,3-dicarboxylic acid , Hydroxyl-containing (meth) acrylate esters, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, hydroxystyrene, such as o, m, or p-hydroxy Oxystyrene, or vinylbenzyl alcohol, such as 4-vinyl benzyl alcohol.

Preferably, the compound has formula (II) or (III):

In the above formula

R ² , R ³ , and R ⁴ are each independently H, F, C _1-10 alkyl, or C _1-10 fluoroalkyl;

n is 1 or 2;

AO is a C _3-20 vinyl carboxylate group, a hydroxy-containing C _5-20 vinyl carboxylate group, or a C _7-20 vinyl aryloxy compound;

G ⁺ is an organic or inorganic cation.

More preferably, the compound has formula (IV), (V), (VI), (VII), or (VIII):

In the above formula

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are independently of each other H, F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl;

Each R ⁸ is independently F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl;

L is a halogenated or non-halogenated C _1-30 alkylene group, C _2-30 alkenylene group, monocyclic or polycyclic C _3-30 cycloalkylene group, monocyclic or polycyclic C _{6- 30} arylene group, or monocyclic or polycyclic C _7-30 alkylene-arylene group;

k and l are independently of each other an integer from 0 to 5 and if k is 0, l is 1;

m is an integer from 0 to 4;

n is 1, 2 or 3;

G ⁺ is an organic or inorganic cation.

The compound may more preferably be of formula (IX), (X), (XI), (XII), or (XIII):

In the above formula

R ⁵ and R ⁷ are independently H, F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl;

G ⁺ is an organic or inorganic cation.

Preferably, R ⁵ and R ⁷ are independently H or -CH ₃ .

In addition to the anionic structure provided by the reaction of sultone with a nucleophile, the monomer comprises a cation G ⁺ , which may be a cation associated with the nucleophile (ie, the cation of a salt of a nucleophile). In this way, the cation may be, for example, an alkali metal cation such as lithium, sodium, potassium, rubidium, cesium, alkaline earth metal cation such as inorganic cations including magnesium, calcium, barium, or strontium; Main group metal cations such as aluminum, tin, lead, or bismuth, or transition metal cations such as inorganic cations including copper, zinc, iron, nickel, cobalt, or silver; Ammonium cations wherein the cations include alkylammonium, including ammonium, mono-, di-, tri-, and tetraalkylammonium such as triethylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, or cetylammonium; Iminium ions; Guanidinium ions, alkylphosphonium cations; Or organic cations such as onium cations of iodine or sulfur substituted with alkyl, aryl, or aralkyl groups. Combinations comprising at least one of the foregoing may be used. Preferably, the cation is a photodegradable onium cation and thus the monomer is also photodegradable, ie a photoacid generator (PAG) monomer.

The PAG monomers disclosed herein are based on a cation-anion structure wherein the cation is preferably an aryl-substituted onium (ie di-substituted iodonium or trisubstituted sulfonium) cation, such as triphenyl sulfonium cation. Or a heterocyclic structure in which a substituent aryl group is further attached to one or more adjacent aryl groups, eg, onium, or exist as part of a fused aromatic ring system.

   When the monomer is photodegradable, i.e., when the reaction product of the oxyanion nucleophile and sultone is a salt having a first, non-photodegradable cation, the process of the present invention comprises a first, non-photodegradable cation of formula (XIV) Further comprising exchanging with a second cation of:

Where

X is S or I,

Each R ⁰ is independently a halogenated or non-halogenated group comprising a C _1-30 group; _Polycyclic or monocyclic C _3-30 cycloalkyl groups; _Polycyclic or monocyclic C _6-30 aryl groups; Or a combination comprising at least one of the foregoing,

When R ⁰ is each independently a monocyclic C _6-30 aryl group, optionally two R ⁰ groups are further attached to the other by a single bond,

a is 2 or 3, when X is I, a is 2, or when X is S, a is 3.

Preferably, G has the formula (XV), (XVI), or (XVII):

In the above formula

X is I or S,

R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² independently of one another are hydroxy, nitrile, halogen, C _1-10 alkyl, C _1-10 fluoroalkyl, C _1-10 alkoxy, C _1-10 fluoroalkoxy , C _6-20 aryl, fluoro C _6-20 aryl, C _{6 -20} aryloxy, or C _{6 to-20-fluoro} and aryloxy,

Ar ¹ and Ar ² are independently C _10-30 fused or single bonded polycyclic aryl groups;

R ¹³ is a lone pair when X is I or a C _6-20 aryl group when X is S;

p is an integer of 2 or 3, where X is I, p is 2, and when X is S, p is 3,

q and r are independently of each other an integer of 0 to 5,

s and t are each independently an integer from 0 to 4.

Exemplary PAG cation G ⁺ includes the following structural formula:

In the above formula

X is S or I, provided that when X is I, R 'is a lone pair and R is C _1-10 alkyl, C _1-10 fluoroalkyl, C _1-10 alkoxy, or C _1-10 fluoro An alkoxy group, when X is S, R 'is a C _6-30 aryl, a C _6-30 arylene, or a C _7-20 alkyl-aryl group,

R ″ independently of each other is H, OH, halogen, C _1-20 alkyl, C _1-20 fluoroalkyl, C _1-20 alkoxy, C _1-20 fluoroalkoxy, C _3-20 cycloalkyl, C _{3- 20} fluorocycloalkyl, C _6-20 aryl, C _7-20 alkyl-aryl, or a combination comprising at least one of the foregoing,

R ″ 'independently of one another is H, C _1-20 alkyl, C _1-20 fluoroalkyl, C _1-20 alkoxy, C _1-20 fluoroalkoxy, C _3-20 cycloalkyl, C _3-20 fluoro Cycloalkyl, C _6-20 aryl, C _7-20 alkyl-aryl, or a combination comprising at least one of the foregoing.

Examples of monomers of formula (I) include the following:

Wherein R ⁵ is H, F, C _1-6 alkyl, or C _1-6 fluoroalkyl. Preferably, R ⁵ is H or -CH ₃ .

The aforementioned monomers can be prepared from nucleophiles having a precursor sultone of formula (XVIII) and a polymerizable group:

R in formula (XVIII) is independently of each other F, C _1-10 alkyl, fluoro-substituted C _1-10 alkyl, C _1-10 cycloalkyl, or fluoro-substituted C _1-10 cycloalkyl, Provided that at least one R is F. If R or other substituents are not specified at all for a carbon atom, it will generally be understood in the present invention that the valence of each such carbon atom is filled with hydrogen atom (s). Exemplary group R is, in addition to one or more fluorine atoms, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl , 2-methylbutyl, 3-methylbutyl, n-hexyl, n-heptyl, n-octyl, 3-octyl, n-decyl, or fluoromethyl group, 2,2,2-trifluoroethyl, perfluoro Any of the foregoing alkyl groups having one or more fluorine substituents, including roethyl, perfluorobutyl, and the like; Or cycloalkyl groups such as cyclobutyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 1- or 2-adamantyl, 1- or 2-decalinyl; Or any of the aforementioned alkyl groups having one or more fluorine substituents, including perfluorocyclopentyl, 3,5-bis (trifluoromethyl) cyclohexyl, perfluorocyclohexyl, and the like. More preferably, R is F.

In formula (XVIII), n is an integer of 0 to 10, and preferably n is 1, 2, or 3. Sultone may comprise m substituents R, wherein m is an integer from 1 to 4 + 2n. The sultone may comprise only a single R group substituent (where the substituent is F and n is 1), or one or more substituents may be included outside the F group, and the total number of substituents R may be 2 + n Where limited, each ring carbon herein has up to two substituents for up to 2 × (2 + n) or 4 + 2n substituents. Preferably, the total number of substituents is limited to the case where m is an integer of 1-4. Otherwise m is 0 and / or R is not F.

Preferably, the sultone is of formula (XIX), (XX), or (XXI):

Wherein each R is independently F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl, provided that at least one R is F; a is an integer of 1-6, b is an integer of 1-8, c is an integer of 1-10.

More preferably, sultone is of formula (XXII):

Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are independently of each other H, F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl, provided that R ¹⁴ , R ¹⁵ , R ^At least one of ¹⁶ , and R ¹⁷ is F;

Preferably, at least one of R ¹⁴ , R ¹⁵ , or R ¹⁶ may be a fluorine atom, wherein the remaining R ¹⁴ , R ¹⁵ , and / or R ¹⁶ are each H and R ¹⁷ is H. Also preferably, both R ¹⁴ , R ¹⁵ and / or R ¹⁶ are fluorine atoms, with the remaining R ¹⁴ , R ¹⁵ , and / or R ¹⁶ being H and R ¹⁷ is H.

Even more preferably, the sultone may be of formula (XXIII) or (XXIV):

Wherein R ¹⁵ and R ¹⁶ are independently of each other H, F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl, provided that at least one of R ¹⁵ or R ¹⁶ is F. Preferably, at least one of R ¹⁵ or R ¹⁶ may be a fluorine atom, wherein the remaining R ¹⁵ and / or R ¹⁶ are each H. Also preferably, R ¹⁵ and R ¹⁶ both comprise fluorine, with the remaining R ¹⁵ and / or R ¹⁶ being H.

Exemplary sultones of formula (XVIII) include those of the formula:

Sultones can generally be prepared by themselves by dehydrating cyclization of the precursor alpha-omega alcohol-sulfonic acid compound in the presence of heat. The cyclization reaction can be carried out at a temperature up to 250 ° C, preferably at 50 to 200 ° C. Heating at these temperatures can be carried out for the time necessary to effect cyclization in sufficient yield. Azeotropic dehydration can also be used to remove water (e.g., using benzene / water or toluene / water) from the solution forming the water azeotrope, or to remove the water generated during the cyclization reaction. While reactive distillation can be used. Alternatively, a dehydrating agent such as 1,3-dicyclohexylcarbodiimide can be used, or the cyclization can be carried out under dehydrating acidic conditions such as anhydride (eg acetic anhydride) or sulfuric acid.

Alpha-omega sulfonic acid compounds that can be cyclized to form sultone can be prepared by themselves in the same manner as for forming sulfinic acid from the corresponding alpha-omega hydroxy-bromo compound. In this reaction, the bromine group is substituted with sodium dithionite (Na ₂ S ₂ O ₄ ) in the presence of a weak base such as sodium bicarbonate to form an intermediate alpha-omega hydroxy sulfinate and then the sulfinate to the corresponding sulfonate Oxidize. Oxidation of sulfinates can be carried out using a suitable method, for example by oxidation using an aqueous solution of a peroxide such as aqueous potassium permanganate or hydrogen peroxide. The alpha-omega hydroxy sulfonate salt can then be treated directly with an acid or converted to the corresponding sulfonic acid by protonation using a solid acid source such as a cation-exchange resin. Such useful resins are sulfonic acid strong cation exchange resins, such as AMBERLITE ™ 120H or AMBERLYST ™ 15H resins, available from Rohm Hass Company.

The method for producing the monomer of the present invention is to react sultone with a nucleophile as described above. The reaction used in this context means adding nucleophiles to carbon alpha against sulfone oxygen with ring opening. Preferably, the nucleophile is an oxygen anion of a carboxy- or hydroxy-containing halogenated or non-halogenated C _2-30 olefin-containing compound. More preferably, the nucleophile is C _3-20 vinyl carboxylic acid, C _8-20 vinyl aromatic carboxylic acid, hydroxy-containing C _5-20 vinyl carboxylate, hydroxy-containing C _5-20 vinyl ether or precursors thereof, or C _7-20 is the oxygen anion of a vinyl hydroxyaromatic compound. When used, the hydroxyaromatic compounds may comprise phenolic hydroxy groups, or non-phenolic hydroxy groups such as benzyl hydroxy groups, or pendant hydroxy groups.

Oxygen anions are formed by reacting a hydroxy-containing halogenated or non-halogenated C _2-30 olefin-containing compound with a base having a pKa greater than 12 for the conjugate base, provided that the base used is a protonated precursor of the nucleophile Is sufficiently basic to deprotonate, and the base itself is non-nucleophilic and does not cause a significant reaction with other functionalities in the nucleophile. Bases useful for this purpose include carbonate bases such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium bicarbonate, and guanidinium, depending on the acidity of the protons to the conjugate acid of the nucleophile; Hydroxide bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; Alkoxide bases such as sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium amylate, or potassium t-butoxide; Amido bases such as lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, lithium hexamethylsilazide, sodium hexamethylsilazide, potassium hexamethylsilazide; Amine bases such as trimethylamine, triethylamine, diethylisopropylamine, diisopropylamine, t-butylamine, proton sponge, cyclohexylamine, aniline, pyridine, N, N-dimethylaminopyridine, 4-pi Lolidinepyridine, pyrazine, pyrrole, piperidine, N-methyl piperidine, 2,2,6,6-tetramethylpiperidine, tetramethylethylene diamine, diaminocyclohexane, N, N, N'N '-Tetramethylcyclohexane, diazabicyclononane (DBN), diazabicycloundecane (DBU), and Troger's base; Hydride bases such as lithium hydride, sodium hydride, potassium hydride, rubidium hydride, cesium hydride, calcium hydride; Grignard reagent or organolithium reagent, such as methyl magnesium chloride or n-butyllithium; Li, Na, K, Rb, and Cs that react directly with alkali metals, for example nucleophiles, or are dissolved in a medium such as ammonia (Li / NH ₃ ) or graphite (eg KC ₈ ). Preferably, the oxygen anion is selected from hydroxides (eg NaOH or KOH), alkoxides (eg sodium ethoxide or potassium t-butoxide), carbonates (eg Na ₂ CO ₃ , or NaHCO ₃ ) or hydrides (NaH or KH) using a base. If the oxygen anion is an anion of phenol or alcohol, the reaction conditions are most preferably deprotonation of alcohol / phenol with NaH or KH in a nonpolar, non-enolated solvent.

The reaction of sultone with nucleophiles can be carried out in a solvent. Solvents useful for this purpose include water, ammonia, ethers such as ethyl ether, diisopropyl ether, methylphenyl ether, diphenyl ether, tetrahydrofuran, dioxane, or dioxolane; Alcohols such as methanol, ethanol, isopropanol, t-butanol, 2-methylpropanol, methyl cellosolve, or ethyl cellosolve; Acetonitrile; Amides such as N, N-dimethylformamide, N, N-dimethyl acetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and hexamethyl phosphoramide; Dimethylsulfoxide, and sulfolane. The reaction conditions are not particularly limited and may be carried out at a temperature of about 250 ° C. or less for a suitable time for carrying out the ring opening addition reaction.

PAG cations can be included in the monomer, and sometimes can be carried out by a cation exchange reaction, it referred to as a metathesis reaction, wherein the first cation / anion pair A ⁺ C ^- the second cation / anion pair B ⁺ D ^- reaction in the solution to form a ^- to exchange the product a ⁺ D ^- and B ⁺ C. Metathesis (ie, ion exchange) reactions can be carried out, for example, in a dual phase medium, where low-active cations / high-active anions such as, for example, triphenylsulfonium bromide, are for example (4- And high-active cations / low-active anions such as sodium or potassium salts of sulfo-3,3,4,4-tetrafluorobutyl-2-methyl-2-propenoate). The biphasic medium may be any suitable biphasic medium and preferably has an aqueous phase for dissolving and removing the resulting high-active salts (e.g. NaBr or KBr in the illustrative examples) and organic media such as ethers. Or preferably dissolve and remove low active salts (eg, triphenylsulfonium salts of 4-sulfo-3,3,4,4-tetrafluorobutyl-2-methyl-2-propenoate) In order to be dichloromethane. The exchange can be carried out at ambient temperature for a time suitable to effect the exchange equilibrium, where the solvent, amount, and time can be determined by the skilled person.

Monomers comprising the PAG monomers disclosed herein may be polymerized with comonomers suitable for copolymerization with them. Preferably, when the monomer is a PAG monomer, other comonomers and copolymers for polymerizing the PAG monomer to provide one or more comonomers having acid-sensitive groups, other properties such as etching control, dissolution rate control, and adhesion To form. Such copolymers may be useful for photoresists, preferably EUV lithography, and may preferably have specific absorbance and resolution characteristics over different wavelengths of radiation when exposed to EUV radiation. For example, EUV radiation sources outside the emission spectrum in the EUV region (about 12-14 nm, where the typical emission used is 13.4-13.5 nm) can emit at longer wavelengths, 248 nm and / or 193 nm. (As is also the emission band for the KrF and ArF excimer lasers used in DUV and 193 nm lithography), the photoasheet generator may be sensitive to this.

The invention is further illustrated by the following examples.

All compounds used herein are commercially available except where a process is provided below. Nuclear magnetic resonance (NMR) spectra are obtained using a Varian INOVA 300 (FT 300 MHz, ¹ H; 282 MHz, ¹⁹ F) spectrometer. Chemical shifts for the ¹ H and ¹⁹ F spectra are internally referenced to tetramethylsilane or internal solvent resonance and reported for tetramethylsilane. 4-bromo-3,3,4,4-tetrafluoro-1-butanol is obtained from Synquest Laboratories. All reagents are obtained from Aldrich unless otherwise specified. Solvents are obtained from Aldrich or Fisher Scientific.

Thermogravimetric analysis (TGA) is obtained using a TA Instruments Q5000 Thermogravimetric Analyzer operating at a temperature ramp rate of 5 ° C./min under nitrogen.

X-ray crystallographic data is obtained using the Bruker SMART X2S benchtop crystallography system. Use APEX2 Version 2009.9 software (Bruker AXS Ins.) For preliminary measurement of unit cells. Measurement of integral intensity and unit cell refinement is performed using SAINT Version 7.68A software (Bruker AXS Inc., 2009). Data is corrected for absorption effect using multiscan technology with SADABS Version 2008/1 software (Bruker AXS Inc.).

Example 1

Preparation of 2-methyl-2-propenoic acid, 4-sulfo-3,3,4,4-tetrafluorobutyl ester, sodium salt (1: 1)

A. Preparation of Sodium 4-hydroxy-1,1,2,2-tetrafluorobutane-1-sulfinate intermediate

4-Bromo-3,3,4,4-tetrafluoro-1-butanol (5.00 g, 22.2 mmol) was added NaHCO ₃ (5.60 g, 66.67 mmol) and Na in 15 ml of acetonitrile and 22 ml of water. _To a slurry of ₂ S ₂ O ₄ (11.61 g, 66.67 mmol). The mixture is heated with stirring in a wax bath at about 55 ° C. for 2 days. The slurry was allowed to settle down and an aliquot recovered to indicate completion of the reaction by ¹ H NMR (D ₂ O). The reaction mixture is filtered and the volatiles are removed on a rotary evaporator under reduced pressure to give the sulfinate salt intermediate as a white solid, which is again placed in a wax bath and heated over weekend at 80 ° C. under reduced pressure. ¹⁹ F NMR spectra confirm the identity of the sulfinate salt intermediate. ¹⁹ F NMR (D ₂ O) d-112.55 (dd, 2F), -131.30 (dd, 2F).

B. Preparation of Sodium 4-hydroxy-1,1,2,2-tetrafluorobutane-1-sulfonate intermediate (small scale)

The prepared solid is dissolved in 25 ml of water, cooled to 0 ° C. and 5 ml of 50% aqueous H ₂ O ₂ (w / w) is added under steam evolution. After stirring for 1 hour, the NMR spectrum of the aliquots taken indicates that the reaction was about 50% complete. Add an additional amount (5 mL) of H ₂ O ₂ and continue stirring. NMR analysis indicates the reaction is complete. The volatiles are removed on a rotary evaporator under reduced pressure to give a white solid. Peroxide test strips are used to confirm the presence of peroxides in the condensate, discard them, and dissolve the solids again in water. Sodium bisulfite is added until no peroxide remains. The slurry is filtered and the volatiles are removed on a rotary evaporator to yield the sulfonate salt as a white solid. ¹⁹ F NMR (D ₂ O) d-112.44 (dd, 2F), -117.08 (dd, 2F).

C. Preparation of Sodium 4-hydroxy-1,1,2,2-tetrafluorobutane-1-sulfinate intermediate (larger scale)

4-Bromo-3,3,4,4-tetrafluoro-1-butanol (19.92 g, 88.54 mmol) was dissolved in 60 mL acetonitrile and 88 mL water in NaHCO ₃ (22.31 g, 265. 6 mmol) and Na _To a slurry of ₂ S ₂ O ₄ (46.25 g, 265.6 mmol). The mixture is heated at about 55 [deg.] C. for 2 days in a wax bath without stirring because of the large amount of solids present. ¹⁹ F NMR spectra showed little conversion to the product. The temperature is then raised to about 80 ° C. As the temperature is increased, a sufficient amount of inorganic salts (NaHCO ₃ and Na ₂ S ₂ O ₄ ) are dissolved to allow the mixture to stir. Additional amount of sodium dithionite (17 g) and sodium bicarbonate (15 g) are added. NMR spectrum indicates that further reaction has taken place. The reaction mixture is cooled to ambient temperature and additional amount of water (100 mL) and acetonitrile (100 mL) is added to dissolve all solid material. NMR spectra are taken for each layer. The aqueous layer contains sulfinate and possibly a small amount of sulfonate, but without starting bromide, the acetonitrile layer showed a significant amount of starting material. Separate the layers. The aqueous layer is set aside and an additional amount of sodium dithionite (30 g) and sodium carbonate (38 g) is added to the acetonitrile layer (200 mL) with about 100 mL of water. The reaction mixture is heated at about 85 ° C overnight. The solution is cooled, filtered and combined with the separated aqueous layer first to remove volatiles on a rotary evaporator. The resulting crunch-phase solid is washed with about 200 mL of ether and dried under vacuum.

D. Preparation of Sodium 4-hydroxy-1,1,2,2-tetrafluorobutane-1-sulfonate intermediate (larger scale)

The solid prepared above is dissolved in 25 mL of water, cooled to 0 ° C. in an ice bath and then 50 mL of aqueous 50% H ₂ O ₂ (w / w) is added under steam evolution. The reaction mixture is stirred overnight. ¹⁹ F NMR spectra showed that the reaction was about 90-95% complete. Add an additional amount (20 mL) of H ₂ O ₂ solution and continue stirring until NMR analysis shows the reaction is complete. Sodium bisulfite is then added until no peroxide remains. The slurry is then filtered and the volatiles are removed on a rotary evaporator to yield a white solid having the same characteristic characteristics as described in Example 1, part B.

E. Preparation of 4-hydroxy-1,1,2,2-tetrafluorobutane-1-sulfonic acid intermediate

The white solid from Example 1, Part D, containing sodium 4-hydroxy-1,1,2,2-tetrafluorobutane-1-sulfonate, was extracted with methanol (about 200 mL) and filtered to form particles. Remove it. The resulting pale yellow solution is passed through a column packed with about 8 cm of AMBERLITE ™ 120H acidic cation exchange resin to obtain a pale brown solution of the compound protonated with sulfonic acid. An additional amount of methanol is used to flush the remaining sulfonic acid. The volatiles were removed under reduced pressure to give a dark brown oil containing black particle specifications. The yield was 15.5 g, 77.2% based on the starting material 4-bromo-3,3,4,4-tetrafluoro-1-butanol.

The sulfonic acid is characterized by thermogravimetric analysis (TGA) under a nitrogen atmosphere and at a temperature ramping rate of 5 ° C./min. Figure 1 shows the thermogravimetric analysis (TGA) plot data, where it can be seen that the decomposition proceeds steadily, losing about 30% of the weight until the decomposition of sulfonic acid reaches about 150 ° C. At a temperature of 159.6 ° C., the maximum decomposition rate is reached, and at about 245 ° C., the compound reaches full weight loss.

F. Preparation of 3,3,4,4-tetrafluorobutanesultone

4-hydroxy-1,1,2,2-tetrafluorobutane-1-sulfonic acid (2.00 g, 8.84 mmol) is placed in a 5 mL round bottom flask with a short distillation column. The system is placed under a nitrogen atmosphere. The flask is immersed in a hot wax bath and the temperature is gradually raised from 130 ° C to 180 ° C. As the temperature is raised as above, water begins to distill to the cooler zone of the distillation apparatus. The apparatus is dismantled and the flask is reconnected to the microdistillation apparatus and heating resumes under nitrogen. The pressure is gradually reduced to distill the product sultone and water to form two phase liquid product. The lower sultone layer is recovered by pipette, dried over anhydrous magnesium sulfate and filtered through a pipette filter to give the product as a colorless liquid.

G. Preparation of 3,3,4,4-tetrafluorobutanesulfone (larger scale)

4-hydroxy-1,1,2,2-tetrafluorobutane-1-sulfonic acid (6.78 g, 30.0 mmol) is placed through a V-tube into a 50 mL round bottom flask attached to a Schlenk tube. The system is placed under vacuum and the Schlenk tube is immersed in liquid nitrogen. The flask containing sulfonic acid is immersed in a hot wax bath and the temperature is gradually raised to about 160 ° C. The product sultone and water are distilled and frozen in the receiver vessel. After thawing, two layers are formed. The lower sultone layer was recovered by pipette and dried over anhydrous magnesium sulfate and then filtered to give the product as a colorless liquid (3.85 g, 61.7%).

H. Preparation of 2-methyl-2-propenoic acid, 4-sulfo-3,3,4,4-tetrafluorobutyl ester, sodium or potassium salt (1: 1)

Sodium salt (1: 1): sodium hydride (0.029 g, 1.2 mmol), on an NMR tube scale, is slowly added to methacrylic acid (0.103 g, 1.2 mmol) in 1 mL of CD ₃ CN. After stirring overnight, 3,3,4,4-tetrafluorobutanesultone (0.250 g, 1.2 mmol) is added and the mixture is transferred to an NMR tube. The progress of the reaction is monitored by ¹ H NMR. The mixture is gradually heated to 75 ° C. at which time the reaction is complete.

Potassium salt (1: 1): methacrylic acid (1.708 g, 19.85 mmol) in bulk scale is slowly added to potassium hydride (1.150 g, 28.66 mmol) in 40 mL of THF. After stirring overnight, the reaction mixture is filtered and the volatiles are removed under reduced pressure. 3,3,4,4-tetrafluorobutanesultone (3.260 g, 15.66 mmol), methacrylic acid (2.0 mL), and a small amount of hydroquinone are added to the potassium methacrylate and the mixture is heated at 75 ° C overnight. Acetone (10 mL) is added to the mixture. The solid is filtered off, washed with an additional amount of acetone and dried under reduced pressure. The solid is then extracted with water and filtered. The volatiles are removed under reduced pressure to give a white crystalline solid (4.10 g, 78.8%).

2 shows the ORTEP plot of the structure of the product, 2-methyl-2-propenoic acid, 4-sulfo-3,3,4,4-tetrafluorobutyl ester, potassium salt (1: 1). Example 1, An aqueous solution of the product of the H portion (bulk scale) is evaporated to grow crystals suitable for single crystal x-ray diffraction studies. Crystals grow into flat, colorless needles. The data set is collected in a simple manner using the Bruker SMART X2S benchtop crystallography system. The XPREP Version 2008/2 software (Bruker AXS Inc.) determines that the space group is P 1 21 / c 1, Z = 4 for the chemical unit, C ₈ H ₉ F ₄ KO ₅ S. The structure is interpreted with XS Version 2008/1 software (Bruker AXS Inc.) and subsequent structure refinement is performed with XL Version 2008/4 software (Bruker AXS Inc.). The final anisotropic full-matrix least-squares refinement for F _o ¹ with 173 variables was concentrated at R ₁ = 5.11% for the observed data and R ₂ = 16.75% for all data.

Example 2

Preparation of Triphenylsulfonium 1,1,2,2-tetrafluoro-4- (methacryloyloxy) butane-1-sulfonate

Potassium 1,1,2,2-tetrafluoro-4- (methacryloyloxy) butane-1-sulfonate (2 g, 6.02 mmol) and triphenylsulfonium bromide (2.25 g, 6.57 mmol) Add to a 100-mL round bottom flask with mL of dichloromethane and 15 mL of distilled, deionized water. The mixture is vigorously stirred for 36 hours. Stop stirring and separate the mixture into two solid layers; The organic layer is washed twice with 30 mL of 1% (w / w) aqueous ammonium hydroxide solution and 5 times with 30 mL of distilled, deionized water. The organic layer is dried over sodium sulfate and filtered. Hydroquinone (1 mg) is added and the solvent is removed under rotary evaporator and high vacuum to give the product as a colorless viscous oil (2.65 g, 4.76 mmol). ¹ H NMR (d ₆ -acetone): 7.9 (br), 6.1 (s), 5.6 (s), 4.4 (t), 2.8 (m), 1.9 (s); ¹⁹ F NMR (d ₆ -acetone):-112.7 (s), -119.7 (s).

Example 3

Preparation of Phenyl dibenzothiophenium 1,1,2,2-tetrafluoro-4- (methacryloyloxy) butane-1-sulfonate

Potassium 1,1,2,2-tetrafluoro-4- (methacryloyloxy) butane-1-sulfonate (1.91 g, 5.75 mmol) and phenyl dibenzothiophenium bromide (2.14 g, 6.27 mmol) Is added to a 100-mL round bottom flask with 15 mL of dichloromethane and 15 mL of distilled, deionized water. The mixture is vigorously stirred over the weekend. Stop stirring and separate the mixture into two solid layers; The organic layer is washed twice with 30 mL of 1% (w / w) aqueous ammonium hydroxide solution and 5 times with 30 mL of distilled, deionized water. Dichloromethane is removed under rotary evaporator and high vacuum to give the product as a white powder (2.41 g, 4.35 mmol). ¹ H NMR (d ₆ -acetone): 8.6 (d), 8.4 (d), 8.0 (t), 7.8 (br), 7.6 (t), 6.1 (s), 5.6 (s), 4.4 (t), 2.8 (m), 1.9 (s); ¹⁹ F NMR (d ₆ -acetone):-112.7 (s), -119.8 (s).

Example 4

Copolymerization of triphenylsulfonium 1,1,2,2-tetrafluoro-4- (methacryloyloxy) butane-1-sulfonate (exemplary polymer)

2-phenyl-2-propyl methacrylate (3.32 g, 16.25 mmol), alpha- (gammabutyrolactone) methacrylate (4.40 g, 23.75 mmol), 3,5-bis (1,1,1,3 , 3-hexafluoro-2-hydroxypropan-2-yl) cyclohexyl methacrylate (3.13 g, 6.25 mmol), and triphenylsulfonium 1,1,2,2-tetrafluoro-4- ( Methacryloyloxy) butane-1-sulfonate (50% by weight in acetonitrile; 4.17 g, 3.75 mmol) is dissolved in 16.8 g of ethyl lactate / cyclohexanone (70/30 v / v). 2,2-Azobis (2,4-dimethylvaleronitrile) (1.24 g, 3.75 mmol) is dissolved in the monomer solution. A small amount (approximately 5 mL) of monomer solution is introduced into a vessel preheated in an 80 ° C. oil bath, after 5 minutes, the remainder of the monomer solution is fed into the vessel over 4 hours. The reaction mixture is heated for a further 2 hours. The reaction solution is cooled to room temperature and precipitated with a 1 L mixture of stirred methyl t-butyl ether and 2-propanol (90/10 v / v). The resulting white powdered polymer is separated by vacuum filtration and dried in a vacuum oven at 45 ° C. for 48 hours (yield 7.3 g, 58%).

Evaluation of Copolymers. DUV evaluation of photoresist containing the polymer of Example 4.

The polymer of Example 4 (0.61 g) was dissolved in 15.40 g of ethyl lactate and 3.82 g of cyclohexanone (70:30 w / w) and 1% of tetramethylammonium salicylate in 0.12 g of ethyl lactate A 1% (w / w) solution of (w / w) solution and 0.06 g of POLYFOX 656 surfactant is added. The solution is filtered through a 0.2 μm TEFLON filter.

The photoresist formulation is lithographically processed as follows. The formulated resist has a base antireflective coating (BARC) using a TEL ACT-8 (Tokyo Electron) coating track (for 248 nm exposure, 60 nm AR ™ 9 antireflective, Rohm and Hass Electronic Materials LLC; or Organic underlayer for EUV 25 nm), spin-coated on a soft-baked 200 mm silicon wafer at 120 ° C. for 60 seconds (for DUV exposure) or at 130 ° C. for 60 seconds (for EUV exposure), approximately 50 nm (DUV In the case of exposure) or 60 nm (in the case of EUV exposure). The photoresist layer was exposed through a photomask using KrF excimer laser (Canon) operating at 248 nm, or EUV radiation (eMET) operating at 13.4-13.5 nm, and the exposed layer was exposed for 60 seconds at 90 ° C. Baking (PEB) process. The coated wafer was then subjected to photoresist for 60 seconds (DUV exposure) or 30 seconds (EUV exposure) with a base developer free of metal ions (obtained from CD-26 Developer, Rohm and Hass; aqueous 0.26N tetramethylammonium hydroxide solution). Develop the layer. The radiation dose versus clear value (E ₀ ) obtained for DUV exposure was 2.7 mJ / cm 2 and 3.6 mJ / cm 2 for EUV exposure.

FIG. 3 shows the DUV contrast curve (plot of film thickness (in angstroms) versus radiation dose (in mJ / cm 2)) for the polymer of Example 4 prepared above. As can be seen from the contrast curve, the radiation dose versus clear (E ₀ ) obtained for the polymer is 2.7 mJ / cm 2.

All ranges disclosed herein are inclusive of the final value, which may be combined independently of one another. As used herein, the suffix "(s)" is intended to include both the singular and the plural of a term being modified, and therefore include at least one of those terms. “Any” or “optionally” means that an event or situation described subsequently may or may not occur, and the description includes cases where an event occurs and an event does not occur. As used herein, “combination” as used herein includes blends, mixtures, alloys, or reaction products. All references are incorporated herein by reference.

The use of the term singular and the similar remarks in the context of the present invention (particularly in the context of the following claims) are considered to encompass the plural, unless the context clearly dictates otherwise or is clearly dismissed by the context. It is also to be understood that the terms "first", "second", and the like herein are used to distinguish elements from one another rather than to indicate order, quantity, or importance.

Claims (10)

Compound of Formula (I):

Where
R ^1, R ^2, and R ³ is independently H, F, a C _{1 -10} alkyl, fluoroalkyl each other - to the substituted C _{1 -10} alkyl, C _{1 -10} cycloalkyl, or fluoro-substituted C _{1 - 10} cycloalkyl, provided that at least one of R ¹ , R ² , or R ³ is F;
n is an integer from 1 to 10;
A is a halogenated or non-halogenated C _2-30 olefin-containing polymerizable group;
G ⁺ is an organic or inorganic cation. The compound of claim 1 having the formula (II) or (III):

Where
R ² , R ³ , and R ⁴ are each independently H, F, C _1-10 alkyl, or C _1-10 fluoroalkyl;
n is 1 or 2;
AO is a C _3-20 vinyl carboxylate group, a hydroxy-containing C _5-20 vinyl carboxylate group, or a C _7-20 vinyl aryloxy compound;
G ⁺ is an organic or inorganic cation. The compound of claim 1 having the formula (IV), (V), (VI), (VII) or (VIII):

In the above formula
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are independently of each other H, F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl;
Each R ⁸ is independently F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl;
L is a halogenated or non-halogenated C _1-30 alkylene group, C _2-30 alkenylene group, monocyclic or polycyclic C _3-30 cycloalkylene group, monocyclic or polycyclic C _{6- 30} arylene group, or monocyclic or polycyclic C _7-30 alkylene-arylene group;
k and l are independently of each other an integer from 0 to 5, and if k is 0, l is 1;
m is an integer from 0 to 4;
n is 1, 2 or 3;
G ⁺ is an organic or inorganic cation. The compound of claim 1 having the formula (IX), (X), (XI), (XII), or (XIII):

In the above formula
R ⁵ and R ⁷ are independently H, F, C _1-10 alkyl, or fluoro-substituted C _1-10 alkyl;
G ⁺ is an organic or inorganic cation. The method according to claim 1, wherein G ⁺ is an alkali metal cation, alkaline earth metal cation, main group metal cation, transition metal cation, ammonium ion, alkylammonium ion, iminium ion, guanidinium ion, alkylphosphonium ion, sulfur or iodine An onium cation, or a combination comprising at least one of the foregoing. The compound of claim 1, wherein G + is a cation having formula (XIV):

In the formula (XIV),
X is S or I,
Each R ⁰ is independently a halogenated or non-halogenated group comprising a C _1-30 group; _Polycyclic or monocyclic C _3-30 cycloalkyl groups; _Polycyclic or monocyclic C _6-30 aryl groups; Or a combination comprising at least one of the foregoing,
When R ⁰ is each independently a monocyclic C _6-30 aryl group, optionally two R ⁰ groups are further attached to the other by a single bond,
a is 2 or 3, where X is I, a is 2, or when X is S, a is 3. The compound of claim 1, wherein G has the formula (XV), (XVI), or (XVII):

Where
X is I or S,
R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² independently of one another are hydroxy, nitrile, halogen, C _1-10 alkyl, C _1-10 fluoroalkyl, C _1-10 alkoxy, C _1-10 fluoroalkoxy , C _6-20 aryl, C _6-20 fluoroaryl, C _6-20 aryloxy, or C _6-20 fluoroaryloxy,
Ar ¹ and Ar ² are independently C _10-30 fused or single bonded polycyclic aryl groups;
R ¹³ is a lone pair when X is I or a C _6-20 aryl group when X is S;
p is an integer of 2 or 3, where X is I, p is 2, and when X is S, p is 3,
q and r are independently of each other an integer of 0 to 5,
s and t are each independently an integer from 0 to 4. A polymer comprising the compound of claim 1. Sultone precursors for monomers having formula (XVIII):

Where
R is independently of each other F, C _1-10 alkyl, fluoro-substituted C _1-10 alkyl, C _1-10 cycloalkyl, or fluoro-substituted C _1-10 cycloalkyl, provided that at least one R is F;
n is an integer of 0-10, m is an integer of 1-4 + 2n. A monomer comprising the reaction product of the sultone precursor of claim 9 with a oxyanion of a carboxy- or hydroxy-containing halogenated or non-halogenated C _2-30 olefin-containing compound.

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